Hybrid vapor phase-solution phase growth techniques for improved CZT(S,Se) photovoltaic device performance

Abstract

A hybrid vapor phase-solution phase CZT(S,Se) growth technique is provided. In one aspect, a method of forming a kesterite absorber material on a substrate includes the steps of: depositing a layer of a first kesterite material on the substrate using a vapor phase deposition process, wherein the first kesterite material includes Cu, Zn, Sn, and at least one of S and Se; annealing the first kesterite material to crystallize the first kesterite material; and depositing a layer of a second kesterite material on a side of the first kesterite material opposite the substrate using a solution phase deposition process, wherein the second kesterite material includes Cu, Zn, Sn, and at least one of S and Se, wherein the first kesterite material and the second kesterite material form a multi-layer stack of the absorber material on the substrate. A photovoltaic device and method of formation thereof are also provided.

What is claimed is: 
     
       1. A method of forming a kesterite absorber material on a substrate, the method comprising the steps of:
 depositing a continuous layer of a first kesterite material on the substrate using a vapor phase deposition process, wherein the first kesterite material comprises copper (Cu), zinc (Zn), tin (Sn), and at least one of sulfur (S) and selenium (Se), wherein the substrate is an oxide material, and wherein the first kesterite material is deposited directly onto the oxide material; 
 annealing the first kesterite material to fully crystallize the first kesterite material such that each grain of the first kesterite material is crystalline, and wherein the first kesterite material, when fully crystallized, forms a protective layer on the oxide material; and 
 depositing a layer of a second kesterite material on a side of the first kesterite material opposite the substrate using a solution phase deposition process, wherein the second kesterite material comprises Cu, Zn, Sn, and at least one of S and Se, 
 wherein the first kesterite material and the second kesterite material form a multi-layer stack of the absorber material on the substrate. 
 
     
     
       2. The method of  claim 1 , wherein the step of depositing the layer of the first kesterite material on the substrate using a vapor phase deposition process comprises the step of:
 contacting the substrate with a Cu source, a Zn source, a Sn source, and at least one of a S source and a Se source under conditions sufficient to form the first kesterite material on the substrate. 
 
     
     
       3. The method of  claim 2 , wherein the conditions comprise a temperature of from about 400° C. to about 450° C., and a pressure of from about 1×10 −11  torr to about 1×10 −3  torr. 
     
     
       4. The method of  claim 1 , wherein the layer of the first kesterite material is formed having a thickness of from about 100 nm to about 300 nm. 
     
     
       5. The method of  claim 1 , wherein the first kesterite material is annealed at a temperature of greater than about 500° C. to crystallize the first kesterite material. 
     
     
       6. The method of  claim 1 , wherein the first kesterite material is annealed at a temperature of from about 550° C. to about 650° C. to crystallize the first kesterite material. 
     
     
       7. The method of  claim 1 , wherein the first kesterite material, once crystallized, has an average grain size of from about 1 μm to about 2 μm. 
     
     
       8. The method of  claim 1 , further comprising the step of:
 doping the first kesterite material with Na by depositing a Na precursor layer on the first kesterite material, and wherein by way of the step of annealing the first kesterite material Na ions from the Na precursor layer diffuse into and dope the first kesterite material. 
 
     
     
       9. The method of  claim 1 , wherein the step of depositing the layer of the second kesterite material on the side of the first kesterite material opposite the substrate using a solution phase deposition process comprises the step of:
 depositing one or more precursor solutions onto the first kesterite material using a spin-coating process, wherein the precursor solutions comprise hydrazine. 
 
     
     
       10. The method of  claim 1 , wherein the layer of the second kesterite material is formed having a thickness of from about 100 nm to about 500 nm. 
     
     
       11. The method of  claim 1 , further comprising the step of:
 annealing the multi-layer stack of the absorber material at a temperature of from about 550° C. to about 650° C. 
 
     
     
       12. The method of  claim 1 , further comprising the step of:
 depositing at least one layer of a third kesterite material on the multi-layer stack of the absorber material using either the vapor phase deposition process or the solution phase deposition process, wherein the third kesterite material comprises Cu, Zn, Sn, and at least one of S and Se. 
 
     
     
       13. The method of  claim 1 , wherein the oxide material is selected from the group consisting of: zinc oxide, zinc oxysulfate, zinc tin oxide, and combinations thereof. 
     
     
       14. A method of forming a photovoltaic device, the method comprising the steps of:
 depositing a continuous layer of a first kesterite material on a substrate using a vapor phase deposition process, wherein the first kesterite material comprises Cu, Zn, Sn, and at least one of S and Se, wherein the substrate is an oxide material, and wherein the first kesterite material is deposited directly onto the oxide material; 
 annealing the first kesterite material to fully crystallize the first kesterite material such that each grain of the first kesterite material is crystalline, and wherein the first kesterite material, when fully crystallized, forms a protective layer on the oxide material; 
 depositing a layer of a second kesterite material on a side of the first kesterite material opposite the substrate using a solution phase deposition process, wherein the second kesterite material comprises Cu, Zn, Sn, and at least one of S and Se, and wherein the first kesterite material and the second kesterite material form a multi-layer stack of an absorber material on the substrate; 
 forming a buffer layer on a side of the multi-layer stack of the absorber material opposite the substrate; and 
 forming a transparent front contact on a side of the buffer layer opposite the multi-layer stack of the absorber material. 
 
     
     
       15. The method of  claim 14 , further comprising the steps of:
 forming metal contacts on a side of the transparent front contact opposite the buffer layer; and 
 forming an antireflective coating on the transparent front contact covering the metal contacts. 
 
     
     
       16. The method of  claim 14 , further comprising the step of:
 depositing at least one layer of a third kesterite material on the multi-layer stack of the absorber material using either the vapor phase deposition process or the solution phase deposition process, wherein the third kesterite material comprises Cu, Zn, Sn, and at least one of S and Se.